| Name | County | Politics | From | To |
| Peter G. Van Winkle | Wood | Republican | 1863 | 1869 |
| Waitman T. Willey | Monongalia | Republican | 1863 | 1871 |
| Arthur I. Boreman | Wood | Republican | 1869 | 1875 |
| Henry G. Davis | Mineral | Democrat | 1871 | 1883 |
| Allen T. Caperton | Monroe | Democrat | 1875 | 1876 |
| Samuel Price | Greenbrier | Democrat | 1876 | 1877 |
| Frank Hereford | Monroe | Democrat | 1877 | 1881 |
| Johnson N. Camden | Wood | Democrat | 1881 | 1887 |
| John E. Kenna | Kanawha | Democrat | 1883 | 1893 |
| Charles J. Faulkner | Berkeley | Democrat | 1887 | 1899 |
| Johnson N. Camden | Wood | Democrat | 1893 | 1895 |
| Stephen B. Elkins | Randolph | Republican | 1895 | 1911 |
| Nathan B. Scott | Ohio | Republican | 1899 | 1911 |
| Davis Elkins | Randolph | Republican | 1911 | 1912 |
| Clarence W. Watson | Marion | Democrat | 1911 | 1913 |
| William E. Chilton | Kanawha | Democrat | 1911 | 1917 |
| Nathan Goff | Harrison | Republican | 1913 | 1919 |
| Howard Sutherland | Randolph | Republican | 1917 | 1923 |
| Davis Elkins | Monongalia | Republican | 1919 | 1925 |
| Matthew M. Neely | Marion | Democrat | 1923 | 1929 |
| Guy D. Goff | Harrison | Republican | 1925 | 1931 |
| Henry D. Hatfield | Cabell | Republican | 1929 | 1935 |
| 1Matthew M. Neely | Marion | Democrat | 1931 | 1941 |
| Rush D. Holt | Lewis | Democrat | 1935 | 1941 |
| Harley M. Kilgore | Raleigh | Democrat | 1941 | 1956 |
| 2Joseph Rosier | Marion | Democrat | 1941 | 1942 |
| 3Hugh Ike Shott, Sr. | Mercer | Republican | 1942 | 1943 |
| Chapman Revercomb | Kanawha | Republican | 1943 | 1949 |
| Matthew M. Neely | Marion | Democrat | 1949 | 1958 |
| 4William R. Laird, III | Fayette | Democrat | 1956 | 1956 |
| Chapman Revercomb | Kanawha | Republican | 1956 | 1959 |
| 5Jack D. Hoblitzell, Jr. | Jackson | Republican | 1958 | 1959 |
| 7Robert C. Byrd | Raleigh | Democrat | 1959 | 2010 |
| 6Jennings Randolph | Randolph | Democrat | 1959 | 1985 |
| John D. Rockefeller IV | Kanawha | Democrat | 1985 | 2014 |
| 8Carte Goodwin | Kanawha | Democrat | 2010 | 2010 |
| 9Joe Manchin III | Marion | Democrat | 2010 | |
| Shelley Moore Capito | Kanawha | Republican | 2015 |
1Resigned to become Governor on January 12,
1941.
2Appointed by Governor M. M. Neely January 13, 1941, to
fill unexpired term of M. M. Neely as U. S. Senator. Served until
November 3, 1942.
3Elected for short term from November 3, 1942, to
January 3, 1943.
4Appointed March 13, 1956, by Governor W. C. Marland to
fill vacancy caused by death of Senator Harley M. Kilgore on
February 29, 1956. Served until November 6, 1956.
5Appointed January 25, 1958, by Governor Cecil H.
Underwood to fill vacancy caused by death of M. M. Neely on January
18, 1958.
6Elected November 4, 1958, to fill unexpired term ending
January, 1961.
7Died on June 28, 2010, while in office.
8Appointed by Governor Joe Manchin, July 16, 2010, to fill unexpired term of Robert C. Byrd until a special election could be held. Served until November 15, 2010.
9Elected November 2, 2010, to fill unexpired term caused by the death of Senator Robert C. Byrd.